EP4355804A1 - Articles façonnés en mousse pu souple - Google Patents

Articles façonnés en mousse pu souple

Info

Publication number
EP4355804A1
EP4355804A1 EP22734246.6A EP22734246A EP4355804A1 EP 4355804 A1 EP4355804 A1 EP 4355804A1 EP 22734246 A EP22734246 A EP 22734246A EP 4355804 A1 EP4355804 A1 EP 4355804A1
Authority
EP
European Patent Office
Prior art keywords
foam
cure
carbon atoms
radicals
formula
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP22734246.6A
Other languages
German (de)
English (en)
Inventor
Daniela HERMANN
Robert Borgogelli
Annegret Terheiden
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Evonik Operations GmbH
Original Assignee
Evonik Operations GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Evonik Operations GmbH filed Critical Evonik Operations GmbH
Publication of EP4355804A1 publication Critical patent/EP4355804A1/fr
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4829Polyethers containing at least three hydroxy groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/16Catalysts
    • C08G18/18Catalysts containing secondary or tertiary amines or salts thereof
    • C08G18/1825Catalysts containing secondary or tertiary amines or salts thereof having hydroxy or primary amino groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08Processes
    • C08G18/16Catalysts
    • C08G18/22Catalysts containing metal compounds
    • C08G18/24Catalysts containing metal compounds of tin
    • C08G18/244Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30Low-molecular-weight compounds
    • C08G18/32Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3271Hydroxyamines
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4833Polyethers containing oxyethylene units
    • C08G18/4837Polyethers containing oxyethylene units and other oxyalkylene units
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40High-molecular-weight compounds
    • C08G18/48Polyethers
    • C08G18/4833Polyethers containing oxyethylene units
    • C08G18/4837Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/485Polyethers containing oxyethylene units and other oxyalkylene units containing mixed oxyethylene-oxypropylene or oxyethylene-higher oxyalkylene end groups
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666Compounds of group C08G18/48 or C08G18/52
    • C08G18/667Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6681Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38
    • C08G18/6688Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/32 or C08G18/3271 and/or polyamines of C08G18/38 with compounds of group C08G18/3271
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00Polymeric products of isocyanates or isothiocyanates
    • C08G18/06Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72Polyisocyanates or polyisothiocyanates
    • C08G18/74Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/12Polysiloxanes containing silicon bound to hydrogen
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/04Polysiloxanes
    • C08G77/38Polysiloxanes modified by chemical after-treatment
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G77/00Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
    • C08G77/42Block-or graft-polymers containing polysiloxane sequences
    • C08G77/46Block-or graft-polymers containing polysiloxane sequences containing polyether sequences
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04Polyurethanes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04Polyurethanes
    • C08L75/08Polyurethanes from polyethers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2101/00Manufacture of cellular products
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00Foam properties
    • C08G2110/0008Foam properties flexible
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00Foam properties
    • C08G2110/0041Foam properties having specified density
    • C08G2110/005< 50kg/m3
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G2110/00Foam properties
    • C08G2110/0083Foam properties prepared using water as the sole blowing agent

Definitions

  • the present invention is in the field of polyurethane (PU) foams. It especially relates to the provision of shaped hot-cure flexible PU foam articles, for example mattresses and/or cushions.
  • PU polyurethane
  • Shaped flexible PU foam articles for example flexible PU foam-containing mattresses and/or cushions, have long been known from the prior art and are employed worldwide. There has been no shortage of attempts to achieve ever greater improvements. The need for optimization has not been fully satisfied to the present day.
  • Shaped flexible PU foam articles for example mattresses, are very bulky and are therefore often compressed, especially compressed and vacuum-packed, for storage and transport due to space considerations. Large distributors are increasingly shipping certain mattresses in compressed and rolled-up form.
  • Such packagings are widely used for mattresses in particular.
  • vacuum packaging the mattress is placed in a bag made of plastic film for example.
  • the thus prepackaged mattress is then placed in a press and compressed with one end of the bag open. The air escapes.
  • the open end of the bag is then welded shut in an airtight manner.
  • the thus obtained vacuum packaging is then rolled up and placed inside an outer bag. The mattress cannot re-expand since the outer bag keeps it in rolled-up form.
  • Flattening a mattress to the extent achieved by a machine during rolling for example requires a force between 40 000 and 250 000 N depending on the mattress. This corresponds to the weight exerted by a mass of 4 to 25 tons.
  • the present invention specifically has for its object to provide shaped flexible PU foam articles such as in particular flexible PU foam-containing mattresses and/or cushions that have good capability of recovering their original shape after compression over a period of at least 20 hours.
  • This invention provides a shaped flexible hot-cure PU foam article, preferably mattress and/or cushion, wherein the hot-cure flexible PU foam has been obtained by reaction of at least one polyol component and at least one isocyanate component in the presence of at least one blowing agent and one or more catalysts that catalyze the isocyanate-polyol and/or isocyanate-water reactions and/or isocyanate trimerization, foam stabilizer and optional further additives, characterized in that the foam stabilizer comprises at least one compound of formula (1):
  • R 1 same or different radicals, selected from the group of alkyl radicals having 1 - 16 carbon atoms or aryl radicals having 6 - 16 carbon atoms or hydrogen or -OR 5 , saturated or unsaturated, preferably methyl, ethyl, octyl, dodecyl, phenyl or hydrogen, more preferably methyl or phenyl
  • R 2 independently identical or different polyethers of the general formula (3) obtainable from the polymerization of ethylene oxide, propylene oxide and/or other alkylene oxides such as butylene oxide or styrene oxide or an organic radical according to formula (4)
  • R 3 same or different radicals, selected from the group of alkyl or aryl radicals, saturated or unsaturated, unsubstituted or substituted with hetero atoms, preferably alkyl radicals having 1 - 16 carbon atoms or aryl radicals having 6 - 16 atoms, saturated or unsaturated, unsubstituted or substituted with halogen atoms, more preferably methyl, vinyl, chlorpropyl or phenyl
  • R 4 divalent organic radical, preferably a divalent organic alkyl or aryl radical, optionally substituted with -OR 5 , more preferably a divalent organic radical of type CpH 2
  • R 5 same or different radicals, selected from the group of alkyl radicals having 1 - 16 carbon atoms or aryl radicals having 6 - 16 carbon atoms, saturated or unsaturated, or hydrogen, preferably alkyl radicals having 1 - 8 carbon atoms, saturated or unsaturated, or hydrogen, more preferably methyl, ethyl, isopropyl or hydrogen
  • R 6 same or different radicals, selected from the group of alkyl radicals having 1 - 18 carbon atoms, and optionally bearing ether functions or substitution with halogen atoms, or aryl radicals having 6 - 18 carbon atoms and optionally bearing ether functions, or hydrogen, preferably alkyl radicals having 1 - 12 carbon atoms, and optionally bearing ether functions or substitution with halogen atoms, or aryl radicals having 6 - 12 carbon atoms and optionally bearing ether functions, or hydrogen, more preferably hydrogen, methyl, ethyl or benzyl
  • R 7 same or
  • the polyether siloxanes according to the invention have different siloxane units which may be combined with one another in the molecule in different ways.
  • the composition of the siloxane units is calculated taking account of the fact that every oxygen atom preferably functions as a bridging member between two silicon atoms in each case, and each silicon atom accordingly only is counted half.
  • the various siloxane units are joined to one another via 2 half oxygen atom (-O1/2O1/2-) groups, as a result an oxygen bridge (-0-) is shown.
  • the linked siloxane block polymers of general average formula (1) are present in the form of a mixture. It is always a distribution of different structures, so that all indicated indices, e.g. a, b, c, d, e, f and g, represent only mean values. Especially y1 , y2 and y3 represent an average value across different structures present in the mixture and as a result the average can be a non-integer number between 0 and 1 .
  • the use of crosslinking molecules providing at least two multiple bonds in the preparation of polyether siloxanes according to formula (1) results in the structural elements that are represented in formula (1) by G.
  • the bridging groups contain (Oi/2)nSiR 1 m -groups that are connected by an organic or Si containing radical.
  • G preferably is represented by independently same or different radicals of type (i), (ii) and (iii) (l) (ii) (iii) with the proviso that the presence of a bridging group with two connected (Oi/2)nSiR 1 m -groups, namely radical (i), is mandatory, preferably all radicals (i), (ii), (iii) are mandatory, with
  • R 10 independently same or different radicals, selected from the group of alkyl radicals having 1 - 16 carbon atoms or aryl radicals having 6 - 16 carbon atoms or hydrogen, preferably selected from the group of alkyl radicals having 1 - 6 carbon atoms or aryl radicals having 6 - 10 carbon atoms or hydrogen, more preferably methyl or hydrogen
  • tri- and tetrafunctional crosslinkers may also be used as bridging groups.
  • the use of at least one compound of formula (1) in the production of flexible hot-cure PU foam enables improved dimension recovery of the shaped hot-cure PU foam article after compression, especially after compression and vacuuming.
  • mattresses are very particularly preferred in the context of the present invention. This advantageously also applies to all of the preferred embodiments of our invention.
  • the shaped hot-cure flexible PU foam article thus provided using the inventive compound(s) of formula (1) therefore has good capability of recovering its original shape even after extended compression over a period of at least 20 hours, especially after compression and vacuuming.
  • the shaped hot-cure flexible PU foam articles in question are particularly low in emissions with regard to volatile organic compounds.
  • the flexible PU foam that results in accordance with the invention preferably has an emission of > 0 pg/m 3 to ⁇ 500 pg/m 3 , more preferably ⁇ 200 pg/m 3 , even more preferably ⁇ 100 pg/m 3 , appropriately determined by the test chamber method based on DIN standard DIN EN ISO 16000-9:2008-04, 24 hours after test chamber loading. This method is described precisely in EP 3205680A1 , specifically in paragraph [0070], which is hereby incorporated by reference.
  • a further advantage is that the shaped hot-cure flexible PU foam articles in question can also meet emissions specifications such as CertiPur and/or VDA 278. What is meant here by low in emissions according to CertiPur is that total emissions of volatile organic substances (TVOCs) are preferably less than 500 pg/m 3 , determined according to the method ISO 16000-9 and ISO 16000-11. Further technical details of the requirements for the CertiPUR standard (Version 1 . July 2017) can be found at: https://www.europur.org/images/CertiPUR_Technical_Paper_-_Full_Version_-_2017.pdf. This latter document (Version 1.
  • VDA 278 Low-emission according to VDA 278 is to be understood as meaning that the PU foams meet the specifications of the method Daimler Chrysler PB VWL 709. The VDA 278 method and specification are also described in the examples.
  • PU foams polyurethane foams
  • production thereof are well known to those skilled in the art and, per se, require no further elucidation.
  • the preparation of the polysiloxanes according to formula (1) used in accordance with the invention is known per se. It can be effected, for example, as described in EP0867462B1 , especially paragraphs [0029] to [0034], and EP3219738B1 , especially paragraphs [0139] to [0144], therein. Reference is hereby made explicitly to EP0867462B1 and EP3219738B1 , and especially to its disclosure-content relating to the preparation of the polysiloxanes used in accordance with the invention.
  • the polysiloxanes used in accordance with the invention can generally be prepared by a platinum-catalyzed addition reaction of a siloxane containing a silane hydrogen atom with a linear polyoxyalkylene oxide polyether wherein the linear chain is blocked at one end by an alkyleneoxy group (such as allyloxy or vinyloxy) and bears a hydrogen atom or has been capped, for example, with an alkoxy, aralkyloxy or acyloxy group at the other end.
  • bridging substances are used, which can likewise react in a platinum-catalyzed addition reaction with a siloxane containing a silane hydrogen atom. These are notable in that they have at least two multiple bonds.
  • the resulting structural elements are represented in formula (1) by G.
  • G Especially preferred is the use of trimethylolpropane diallyl ether, butane-1 ,4-diol divinyl ether, diallyl polyethers, dimethallyl polyethers and/or 1 ,3-divinyltetramethyldisiloxane as compounds providing at least two multiple bonds.
  • the preparation of the polysiloxanes according to formula (1) is also demonstrated in the experimental part.
  • siloxanes of formula (1) contain an amount of at least 1% by weight of high molecular weight product proportion with a molecular weight of > 100 000 g/mol, determined by gel permeation chromatography, preferably as described in the experimental part.
  • the proportion with a molecular weight > 100 000 g/mol is at least 3% by weight and in a further preferred embodiment at least 5% by weight.
  • Shaped articles in the context of the invention are shaped bodies of different shape.
  • Preferred shapes in the context of the invention are, for example, geometries such as spheres, cuboids, cylinders etc.
  • Shaped hot-cure PU foam articles in the context of the invention are thus shaped bodies made of polyurethane foam.
  • Particularly preferred shaped flexible hot-cure PU foam articles in the context of the present invention are mattresses and/or cushions and also foam blocks in general.
  • mattresses per se and the production thereof are known. They usually consist of a mattress core, e.g. comprising foam, latex, natural products and/or a spring core, and a cover surrounding the mattress.
  • a mattress and/or cushion is understood to mean that at least one section made of flexible hot- cure PU foam is present in the mattress and/or the cushion.
  • the mattress and/or the cushion can consist entirely of flexible hot-cure PU foam, apart from the cover.
  • polyurethane foam in general is known per se. It is formed by the tried and tested reaction of at least one polyol component and at least one isocyanate component in the presence of at least one blowing agent (e.g. water) in a polyaddition reaction. It is essential to the present invention that the foam is a flexible PU foam and its manufacturing is carried out in the presence of at least one compound of formula (1).
  • the polyurethane foam according to the invention is a hot-cure flexible polyurethane foam, or a combination of these flexible PU foams is used, for example two of these flexible PU foams.
  • the term "flexible hot-cure PU foam” is known per se to the person skilled in the art; this is a fixed technical term which is correspondingly established in the specialist field, but will nevertheless be elucidated briefly here.
  • Flexible PU foams are elastic and deformable and usually have open cells. As a result, the air can escape easily on compression.
  • rigid PU foams that are inelastic and usually have closed cells, are used for insulation purposes and are not in the focus of the present invention.
  • the shaped flexible PU foam article is characterized in that the hot-cure flexible PU foam is a standard flexible PU foam, viscoelastic PU foam or a hypersoft PU foam.
  • the hot-cure flexible PU foam is a standard flexible PU foam.
  • the crucial difference between a flexible hot-cure PU foam and a cold-cure PU foam lies in the different mechanical properties. It is possible to differentiate between flexible hot-cure PU foams and flexible cold-cure PU foams via rebound resilience in particular, also called ball rebound (BR) or resilience.
  • BR ball rebound
  • a steel ball having a fixed mass is allowed to fall from a particular height onto the test specimen and the height of the rebound in % of the drop height is then measured.
  • the values in question for a cold-cure flexible PU foam are preferably in the region of > 50%.
  • Cold-cure flexible PU foams are therefore also often referred to as HR foams (HR: High Resilience).
  • HR foams High Resilience
  • hot- cure flexible PU foams have rebound values of preferably 1 % to not more than 50%.
  • the hot-cure flexible PU foams according to the invention therefore have rebound values of preferably 1 % to not more than 50%, determinable in accordance with DIN EN ISO 8307:2008-03.
  • a further mechanical criterion is the sag or comfort factor.
  • a foam sample is compressed in accordance with DIN EN ISO 2439 and the ratio of compressive stress at 65% and 25% compression is measured.
  • Cold-cure flexible PU foams here have a sag or comfort factor of preferably > 2.5.
  • Hot-cure flexible PU foams have a value of preferably ⁇ 2.5.
  • the hot-cure flexible PU foams of the invention therefore have a sag or comfort factor of preferably ⁇ 2.5, determinable as specified above.
  • hot-cure PU foams and cold-cure PU foams result from differences in the formulation for production of the foams.
  • a cold-cure flexible PU foam predominantly high-reactivity polyols having primary OH groups and average molar mass > 4000 g/mol are usually used.
  • low molecular weight crosslinkers are also used, and it is also possible for the function of the crosslinker to be assumed by higher-functionality isocyanates.
  • hot-cure flexible PU foams comparatively predominantly unreactive polyols having secondary OH groups and an average molar mass of ⁇ 4000 g/mol are preferably used.
  • reaction of the isocyanate groups with the hydroxyl groups thus occurs as early as in the expansion phase (CO2 formation from -NCO and H2O) of the foam.
  • This rapid polyurethane reaction usually leads, as a result of a viscosity increase, to a relatively high intrinsic stability of the foam during the blowing process.
  • Cold-cure flexible PU foams are usually highly elastic foams. Due to the high intrinsic stability, the cells have generally not been opened sufficiently at the end of the foaming operation and the cell structure additionally has to be open by mechanical crushing. In the case of hot-cure flexible PU foams, by contrast, this is typically not necessary. Highly active stabilizers are defined by formula (1) and (5). In the case of hot-cure flexible PU foams according to the invention, a silicone compound of the formula (1) is used in the production. Additionally, a silicone compound of formula (6) might be used optionally.
  • Open-cell hot-cure flexible PU foams preferably have a gas permeability (also called “porosity”) within a range from 0.5 to 6.5 scfm. This is measured by applying a pressure differential and measuring the volume of air that flows through in accordance with ASTM D 3574 (2011-00). The method is elucidated in detail in the examples (see porosity determined by the flow method therein). Scfm (standard cubic feet per minute) is measured under standard conditions (23°C, 100 kPa). Depending on the application, hot-cure flexible PU foams preferably have a foam density between 8 and 80 kg/m 3 .
  • hot-cure flexible PU foams are used as mattresses, mattress constituents and/or cushions, said foams are differentiated according to regional needs, requirements and preferences of consumers.
  • the preferred hot-cure flexible PU foam for mattress applications has a foam density of preferably 20 to 40 kg/m 3 .
  • a specific class of hot-cure flexible PU foams is that of viscoelastic PU foams. These are also known as "memory foam” and exhibit both a low rebound resilience (preferably ⁇ 10%) and a slow, gradual recovery after compression (recovery time preferably 2-10 s). Materials of this kind are well known in the prior art and are highly valued in particular for their energy- and sound-absorbing properties too.
  • Typical viscoelastic flexible foams usually have a lower porosity and a high density (or a high foam density (FD)) compared to other hot-cure flexible PU foams.
  • Cushions have a foam density of preferably 30-50 kg/m 3 and are thus at the lower end of the density scale typical of viscoelastic foams, whereas viscoelastic PU foams for mattresses preferably have a density in the range of 50- 130 kg/m 3 .
  • the hard and soft (low glass transition temperature) segments become oriented relative to one another during the reaction and then spontaneously separate from one another to form morphologically different phases within the "bulk polymer". Such materials are also referred to as "phase-separated" materials.
  • the glass transition temperature in the case of viscoelastic foams is preferably between -20 and +15°C.
  • the glass transition temperature of other hot-cure flexible PU foams and cold-cure flexible PU foams is usually below -35°C.
  • hot-cure flexible PU foams are classified not only according to foam density but often also according to their compressive strength, also referred to as load-bearing capacity, for particular applications.
  • compressive strength CLD compression load deflection
  • 40% in accordance with DIN EN ISO 3386-1 :2015-10 for hot-cure flexible PU foams is preferably in the range of 0.5-8.0 kPa; viscoelastic polyurethane foams preferably have values of 0.1-5.0 kPa, especially 0.5-2.5 kPa.
  • Hypersoft polyurethane foams may be counted among the group of hot-cure flexible PU foam and preferably have values of 0.1 -3.0 kPa, especially 0.5-2.0 kPa.
  • the flexible hot-cure PU foams to be used in accordance with the invention have the following preferred properties in respect of rebound resilience, foam density and/or porosity, namely a rebound resilience of 1% to 50%, measured in accordance with DIN EN ISO 8307:2008-03, and/or a foam density of 5 to 150 kg/m 3 and/or a porosity of 0.5 to 6 scfm, preferably 1.0 to 6.0 scfm. Particular preference is given to all 3 criteria in respect of rebound resilience, foam density and/or porosity, as indicated above, being satisfied.
  • the flexible polyurethane foam used according to the invention has a compressive strength CLD, 40% in accordance with DIN EN ISO 3386-1 :2015-10, of 0.1 to 8.0 kPa.
  • Hot-cure flexible polyurethane foam and the production thereof are known per se.
  • a preferred hot-cure flexible polyurethane foam has, in particular, a compressive strength CLD, 40% in accordance with DIN EN ISO 3386-1 :2015-10, of 0.5 - 8.0 kPa and/or a rebound resilience of 1-50%, measured in accordance with DIN EN ISO 8307:2008-03, and/or a foam density of 8 to 80 kg/m 3 and/or a porosity of 0.5 to 6 scfm, preferably 1.0 to 6.0 scfm.
  • a possible production method is described, for example, in EP 2481770 or EP2182020.
  • a preferred viscoelastic flexible polyurethane foam has, in particular, a glass transition temperature between -20°C and +15°C and/or a compressive strength CLD, 40% in accordance with DIN EN ISO 3386-1 :2015-10, of 0.1 - 5.0 kPa, in particular 0.5 - 3.0 kPa, and/or a rebound resilience of ⁇ 10%, measured in accordance with DIN EN ISO 8307:2008- 03, and/or a foam density of 30 to 130 kg/m 3 and/or a porosity (after crushing the foam) of 0.5 to 6.0 scfm, preferably 1 .0 to 6.0 scfm.
  • the glass transition temperature can be measured by means of dynamic mechanical analysis (DMA) (DIN 53513:1990-03) or by means of differential calorimetry (DSC) (ISO 11357- 2:2013). Strictly speaking, it is a glass transition range which extends over a temperature range. The reported glass transition temperatures are average values.
  • DMA dynamic mechanical analysis
  • DSC differential calorimetry
  • the shaped flexible PU foam article according to the invention especially the mattress according to the invention, in a preferred embodiment of the invention, has a height of at least 1 cm to not more than 50 cm and a width of from at least 20 cm to not more than 300 cm, and a length of at least
  • the shaped PU foam article according to the invention especially the cushion according to the invention, in a preferred embodiment of the invention, may also have a height of at least 1 cm to not more than 40 cm and a width of at least 15 cm to not more than 200 cm and a length of at least
  • 15 cm to not more than 200 cm examples of preferred dimensions being heights in the range from 2 cm to 30 cm, widths in the range from 15 cm to 50 cm, lengths in the range from 15 cm to 50 cm.
  • the shaped flexible PU foam article takes the form of a mattress and preferably the form of a multizone mattress.
  • the different zones differ in terms of, in particular, the respective hardness.
  • Such multizone mattresses and the production thereof are known perse. They are widely sold commercially.
  • the mattress has up to seven zones of differing hardness which extend over the longitudinal direction of the mattress and are given the appropriate width.
  • the mattress has various hardness zones distributed over its area, which are formed, in particular, by cuts and/or hollow spaces in the mattress, this constitutes a further preferred embodiment of the invention.
  • the shaped flexible PU foam article may also be a cold-cure PU foam mattress, a viscoelastic flexible PU foam mattress, a hot-cure flexible PU foam mattress, a PU gel foam mattress, a latex mattress or a box spring mattress, each containing at least a portion made of a flexible hot-cure PU foam according to the invention.
  • These types of mattress are known per se to those skilled in the art and are also marketed worldwide under these names. Mattresses made solely of flexible PU foam are usually referred to on the market simply as foam mattresses.
  • the term mattress as used for the purposes of the present invention also encompasses corresponding mattress coverings and underlays.
  • the shaped flexible PU foam article preferably the mattress, has the feature that based on its starting volume the shaped flexible PU foam article is compressed by at least 20%, preferably at least 30%, in particular at least 40%, and kept in compressed form by an auxiliary means, in particular packaging means, for at least 20 hours.
  • Suitable auxiliary means are bags and/or films such as are known from the field of roll-up mattresses for example.
  • the bags and/or films may be sealed by any desired means, such as by a clip, or by an adhesive tape or by welding.
  • the function of the auxiliary means is that of maintaining the compressed shape until the end user of the shaped flexible PU foam article wishes to use said shaped article again in the normal way. After removal of the auxiliary means, in particular the packaging means, the compressed shaped article expands again and in the optimal case recovers its original shape and size.
  • the present invention makes it possible to allow improved dimensional recovery after compression over a period of at least 20 hours.
  • the shaped flexible PU foam article is in a compressed and vacuum-packed state and in particular is a roll-up mattress in a vacuum-packed and compressed state.
  • the inventive shaped flexible PU foam article is characterized in that the compound of formula (1) is included in a total of 0.05 % to 3.0 % by weight, preferably from 0.07 % to 2.5 % by weight, more preferably 0.10 % to 2.0 % by weight, based on the entire flexible PU foam.
  • the inventive shaped flexible PU foam article has been obtained with additional use of recycled polyols.
  • compression of the foam in the context of the present invention means that the foam is preferably compressed by at least 20%, based on its starting volume, in particular over a period of at least 20 hours.
  • polyurethanes are all reaction products derived from isocyanates, in particular polyisocyanates, and appropriately isocyanate-reactive molecules. These include polyisocyanurates, polyureas, and allophanate-, biuret-, uretdione-, uretonimine- or carbodiimide-containing isocyanate or polyisocyanate reaction products.
  • the isocyanate components used are preferably one or more organic polyisocyanates having two or more isocyanate functions.
  • Polyol components used are preferably one or more polyols having two or more isocyanate-reactive groups, preferably OH-groups.
  • Isocyanates suitable as isocyanate components for the purposes of this invention are all isocyanates containing at least two isocyanate groups. Generally, it is possible to use all aliphatic, cycloaliphatic, arylaliphatic and preferably aromatic polyfunctional isocyanates known per se. Preferably, isocyanates are used within a range from 60 to 350 mol%, more preferably within a range from 60 to 140 mol%, relative to the sum total of the isocyanate-consuming components.
  • alkylene diisocyanates having 4 to 12 carbon atoms in the alkylene radical, e.g. dodecane 1 ,12-diisocyanate, 2-ethyltetramethylene 1 ,4-diisocyanate, 2-methylpentamethylene 1 ,5-diisocyanate, tetramethylene 1 ,4-diisocyanate and preferably hexamethylene 1 ,6-diisocyanate (HMDI), cycloaliphatic diisocyanates such as cyclohexane 1 ,3- and 1 ,4-diisocyanate and also any mixtures of these isomers, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate or IPDI for short), hexahydrotolylene 2,4- and 2,6-diisocyanate and also the corresponding isomer mixtures, and
  • organic diisocyanates and polyisocyanates can be used individually or in the form of mixtures thereof. It is also possible to use isocyanates which have been modified by the incorporation of urethane, uretdione, isocyanurate, allophanate and other groups, called modified isocyanates.
  • Particularly suitable organic polyisocyanates which are therefore used with particular preference are various isomers of tolylene diisocyanate (tolylene 2,4- and 2,6-diisocyanate (TDI), in pure form or as isomer mixtures of various composition), diphenylmethane 4,4'-diisocyanate (MDI), “crude MDI” or “polymeric MDI” (contains the 4,4’ isomer and also the 2,4' and 2,2' isomers of MDI and products having more than two rings) and also the two-ring product which is referred to as “pure MDI” and is composed predominantly of 2,4' and 4,4' isomer mixtures, and prepolymers derived therefrom.
  • tolylene diisocyanate tolylene 2,4- and 2,6-diisocyanate (TDI)
  • MDI diphenylmethane 4,4'-diisocyanate
  • CAde MDI “crude MDI” or “polymeric MDI” (
  • polyols suitable as polyol component for the purposes of the present invention are all organic substances having two or more isocyanate-reactive groups, preferably OH groups, and also formulations thereof.
  • Preferred polyols are all polyether polyols and/or hydroxyl-containing aliphatic polycarbonates which are customarily used for producing polyurethane systems, in particular polyurethane foams, in particular polyether polycarbonate polyols and/or filled polyols (polymer polyols) such as SAN, PHD and PIPA polyols which contain solid organic fillers up to a solids content of 45% or more in dispersed form, and/or autocatalytic polyols which contain catalytically active functional groups, in particular amino groups, and/or polyols of natural origin, known as “natural oil- based polyols” (NOPs).
  • polyether polyols and/or hydroxyl-containing aliphatic polycarbonates which are customarily used for producing polyurethane systems, in particular polyurethane foams, in particular polyether polycarbonate polyols and/or filled polyols (polymer polyols) such as SAN, PHD
  • the polyols for hot-cure flexible PU foam preferably have a functionality of 1.8 to 8 and number-average molecular weights in the range from 500 to 4000 g/mol.
  • the polyols having OH numbers in the range from 25 to 400 mg KOH/g are preferably used.
  • the number- average molecular weights are preferably determined by gel permeation chromatography (GPC), especially using polypropylene glycol as reference substance and tetrahydrofuran (THF) as eluent.
  • the OH numbers can be determined, in particular, in accordance with the DIN standard DIN 53240:1971-12.
  • polystyrene foams Depending on the required properties of the resulting foams, it is possible to use appropriate polyols, as described for example in: EP1770117, W02007111828 or US20070238800. Further polyols are known to those skilled in the art and can be found, for example, in EP0380993 or US3346557.
  • the preferred polyether polyols are obtainable by addition of alkylene oxides to starter molecules, which contain preferably 2 to 8 active hydrogen atoms.
  • Methods that can be found in the state of the art are for example the anionic polymerization of alkylene oxides in the presence of alkali metal hydroxides, alkali metal alkoxides or amines as catalysts, or the cationic polymerization of alkylene oxides in the presence of Lewis acids such as, for example, antimony pentachloride or boron trifluoride etherate, or polymerization using double metal cyanide catalysts.
  • Suitable alkylene oxides preferably contain 2 to 4 carbon atoms in the alkylene radical. Examples are ethylene oxide, 1 ,2- propylene oxide, 1 ,2-butylene oxide and 2,3-butylene oxide; ethylene oxide and 1 ,2-propylene oxide are preferably used.
  • alkylene oxides which contain more carbon atoms, e.g. styrene oxide.
  • the alkylene oxides can be used individually, cumulatively, in blocks, in alternation or as mixtures.
  • Starter molecules used may especially be compounds having at least 2, preferably 2 to 8, hydroxyl groups, or having at least two primary amino groups in the molecule.
  • Starter molecules used may, for example, be water, di-, tri- or tetrahydric alcohols such as ethylene glycol, propane- 1 , 2-diol and propane-1 ,3-diol, diethylene glycol, dipropylene glycol, glycerol, trimethylolpropane, pentaerythritol, castor oil, etc., higher polyfunctional polyols, especially sugar compounds, for example glucose, sorbitol, mannitol and sucrose, polyhydric phenols, resols, for example oligomeric condensation products of phenol and formaldehyde and Mannich condensates of phenols, formaldehyde and dialkanolamines, and also melamine, or amines such as aniline, EDA, TDA, MDA and PMDA, more preferably TDA and PMDA.
  • the choice of the suitable starter molecule depends on the particular application of the resulting polyether polyol in the polyurethane foam production. For example
  • polyether alcohols having secondary hydroxyl groups in amounts of preferably above 50%, more preferably above 90%, are used, especially those having a propylene oxide block or random propylene oxide and ethylene oxide block at the chain end, or those based solely on propylene oxide blocks.
  • Such polyether alcohols preferably have a functionality of 2 to 8, more preferably 2 to 4, number-average molecular weights in the range from 500 to 4000 g/mol, preferably 800 to 4000 g/mol, more preferably 2500 to 4000 g/mol, and typically OH numbers in the range from 20 to 100 mg KOH/g, preferably 40 to 60 mg KOH/g.
  • di- and/or trifunctional polyether alcohols comprising primary hydroxyl groups in amounts of preferably above 50%, more preferably above 80%, in particular those having an ethylene oxide block at the chain end, are additionally also used.
  • Polyols for cold-cure flexible PU foams (“HR polyols") form a part of this category if the molar mass is simultaneously > 4000 g/mol.
  • All polyether alcohols described in the context of this preferred embodiment preferably have a functionality of 2 to 8, more preferably 2 to 5, number-average molecular weights in the range from 500 to 8000 g/mol, preferably 500 to 7000 g/mol, and typically OH numbers in the range from 5 to 100 mg KOH/g, preferably 20 to 60 mg KOH/g.
  • Polyols having primary OH functions are used here in the case of the hot-cure flexible PU foams of the invention, in a preferred embodiment, not alone but rather in combination with polyols having secondary OH groups. Polyols having primary OH functions are used here in the combination, in a preferred embodiment, only to an extent of ⁇ 50%.
  • polystyrene foams preference is given to using mixtures of various, preferably two or three, polyfunctional polyether alcohols.
  • the polyol combinations used here preferably consist of a low molecular weight “crosslinker” polyol having high functionality, preferably having an OH number from 100 to 400 mg KOH/g, and/or a conventional high molecular weight flexible slabstock foam polyol or HR polyol and/or a “hypersoft" polyether polyol, preferably having an OH number of 20 to 40 mg KOH/g, with a high proportion of ethylene oxide and having cell-opening properties.
  • HR polyols are also used in the viscoelastic foam formulation, the proportion by mass thereof in the polyol mixture preferably is ⁇ 50%.
  • recycled polyols are used.
  • a shaped flexible PU foam article that has been obtained with additional use of recycled polyols corresponds to a preferred embodiment of the invention.
  • the use of recycled polyols normally leads to problems with the recovery of shape after roll compression.
  • the use of at least one compound of formula (1) as elucidated in detail in this description, enables the alleviation of this problem.
  • Recycled polyols are polyols that are obtained from PU foam waste. This may be production waste from flexible PU foam production or from flexible PU foam waste after use by the consumer (for example old mattresses). In both cases, PU foam is liquefied by chemical processes. Various processes are useful here, for example, glycolysis, hydrolysis or acidolysis. The liquid recycled polyol obtained can then be reused for production of flexible PU foam. However, such flexible PU foams often feature distinctly adverse mechanical properties, such as resistance to roll compression.
  • One source for further information on the use of recycled polyols in flexible PU foams is the following BMBF research report: https://www.cleaner-production.de/fileadmin/assets/muls/muls/muls/muls/muls.
  • Polyester polyols usable with preference are based on esters of polybasic aliphatic or aromatic carboxylic acids, preferably having 2 to 12 carbon atoms.
  • aliphatic carboxylic acids are succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, decanedicarboxylic acid, maleic acid and fu marie acid.
  • aromatic carboxylic acids are phthalic acid, isophthalic acid, terephthalic acid and the isomeric naphthalenedicarboxylic acids.
  • polyester polyols are obtained by condensation of these polybasic carboxylic acids with polyhydric alcohols, preferably of diols or triols having 2 to 12, more preferably having 2 to 6, carbon atoms, preferably trimethylolpropane and glycerol.
  • Polyether polycarbonate polyols usable with preference are polyols containing carbon dioxide bound in the form of carbonate. Since carbon dioxide forms as a by-product in large volumes in many processes in the chemical industry, the use of carbon dioxide as comonomer in alkylene oxide polymerizations is of particular interest from a commercial point of view. Partial replacement of alkylene oxides in polyols with carbon dioxide has the potential to distinctly lower the costs for the production of polyols. Moreover, the use of CO2 as comonomer is very advantageous in environmental terms, since this reaction constitutes the conversion of a greenhouse gas to a polymer.
  • the preparation of polyether polycarbonate polyols by addition of alkylene oxides and carbon dioxide onto hydrogen functional starter substances by use of catalysts is well known.
  • Various catalyst systems can be used here: The first generation was that of heterogeneous zinc or aluminium salts, as described, for example, in US 3900424 or US 3953383.
  • mono- and binuclear metal complexes have been used successfully for copolymerization of CO2 and alkylene oxides (EP 2337809, EP 2285490, EP 2741855 or WO 2011163133).
  • Suitable alkylene oxides and hydrogen functional starter substances are the same as used for the preparation of carbonate-free polyether polyols, as described above.
  • Polyols usable with preference that are based on renewable raw materials are of increasing interest for production of PU foams with regard to the long-term limits in the availability of fossil resources, namely oil, coal and gas, and against the background of rising crude oil prices, and have already been described many times in such applications (US 8293808, US 8133930, US 9045581 , EP 1620483, US 20020103091 , EP 1888666 and EP 1678232).
  • a number of these polyols are now available on the market from various manufacturers (EP 1537159, EP 1712576, US 20100240860).
  • the base raw material e.g.
  • polystyrene foam soybean oil, palm oil or castor oil
  • polyols have a different impact on properties in the production of polyurethane foam.
  • polyols based on renewable raw materials which are modified in such way that they can be used to an extent of 100% for production of polyurethanes (EP 1537159, EP 1712576); b) polyols based on renewable raw materials which, because of the processing and properties of the final PU foam, can replace the petrochemical-based polyol only in a certain proportion (US 20100240860).
  • a further class of polyols usable with preference is that of the so-called filled polyols (polymer polyols).
  • SAN, PHD and PIPA polyols are found among typical polyol classes.
  • SAN polyols are prepared by grafting with a copolymer based on styrene-acrylonitrile (SAN).
  • PHD (poly-harnstoff dispersion) polyols are highly reactive polyols containing polyurea particles.
  • PIPA (poly-isocyanate poly-addition) polyols are highly reactive polyols containing polyurethane particles, for example formed by in situ reaction of an isocyanate with an alkanolamine in a conventional polyol.
  • the solid content which is preferably between 5% and 45%, based on the polyol, is e.g. responsible for improved cell opening, and so the polyol can be foamed in a controlled manner, especially with TDI, without foam shrinkage.
  • the solid content thus acts as an essential processing aid.
  • a further function is to control and increase the hardness of the PU foams, since the usage of filled polyols allows to obtain foams with increased hardness with an effect depending on the solid content in the final formulation.
  • the formulations with solid containing polyols are distinctly less self-stable and therefore tend to require physical stabilization in addition to the chemical stabilization coming from the crosslinking reaction. Solid containing polyols can be used alone in a formulation or in combaination with unfilled polyols as described above.
  • a further class of polyols usable with preference is of those that are obtained as prepolymers via reaction of a molar excess of polyol with isocyanate, resulting in NCO functional prepolymers.
  • Such prepolymers are preferably used as a solution to obtain a viscosity reduction, e.g. in the polyol corresponding to the polyol used in the preparation of the prepolymers.
  • a further class of polyols usable with preference is that of the so-called autocatalytic polyols, especially autocatalytic polyether polyols.
  • Polyols of this kind are for example based on polyether blocks, preferably on ethylene oxide and/or propylene oxide blocks, and additionally include catalytically active functional groups, for example nitrogen-containing functional groups, especially amino groups, preferably tertiary amine functions, urea groups and/or heterocycles containing nitrogen atoms.
  • Suitable polyols are described, for example, in EP 1268598, EP 1699842, EP 1319034, EP 1817356, EP 1442070, EP 1268598, US 6924321 , US 6762274, EP 2104696, EP 1576026 or EP 2797903 and can be purchased, for example, under the VoractivTM or Lupranol ® trade names.
  • a preferred ratio of isocyanate and polyol, expressed as the index of the formulation, i.e. as stoichiometric ratio of isocyanate groups to isocyanate-reactive groups (e.g. OH groups, NH groups) multiplied by 100, is in the range from 50 to 140, preferably 70 to 135, more preferably 75 to 130.
  • An index of 100 represents a molar reactive group ratio of 1 : 1.
  • catalysts for the purposes ofthe present invention, includes all compounds known from the prior art which are able to catalyze isocyanate reactions and/or are used as catalysts, cocatalysts or activators in the production of polyisocyanate reaction products, in particular polyurethane foams.
  • Catalysts used in the context of this invention may, for example, be any catalysts forthe isocyanate- polyol (urethane formation) and/or isocyanate-water (amine and carbon dioxide formation) and/or isocyanate dimerization (uretdione formation), and/or isocyanate trimerization (isocyanurate formation), and/or isocyanate-isocyanate with CO2 elimination (carbodiimide formation) and/or isocyanate-amine (urea formation) reactions and/or "secondary" crosslinking reactions such as isocyanate-urethane (allophanate formation) and/or isocyanate-urea (biuret formation) and/or isocyanate-carbodiimide (uretonimine formation).
  • Suitable catalysts for the purposes of the present invention are, for example, substances which catalyze one ofthe aforementioned reactions, especially the gelling reaction (isocyanate-polyol), the blowing reaction (isocyanate-water) and/or the dimerization or trimerization ofthe isocyanate.
  • Such catalysts are preferably nitrogen compounds, especially amines and ammonium salts, and/or metal compounds.
  • Suitable nitrogen compounds as catalysts, also referred to hereinafter as nitrogen-containing catalysts, forthe purposes ofthe present invention are all nitrogen compounds according to the prior art which catalyze one of the abovementioned isocyanate reactions and/or can be used for production of polyurethanes, especially of polyurethane foams.
  • suitable nitrogen-containing compounds as catalysts for the purposes of the present invention are preferably amines, especially tertiary amines or compounds containing one or more tertiary amine groups, including the amines triethylamine, triethanolamine, diethanolamine, N,N- dimethylcyclohexylamine, N,N-dicyclohexylmethylamine, N,N-dimethylaminoethylamine, N,N,N‘,N‘- tetramethylethylene-1 ,2-diamine, N,N,N‘,N‘-tetramethylpropane-1 ,3-diamine, N,N,N‘,N‘-tetramethyl- 1 ,4-butanediamine, N,N,N‘,N‘-tetramethyl-1 ,6-hexanediamine, N,N,N‘,N”,N“-pentamethyldiethyl- enetriamine, N,N,N‘-trimethylaminoethyl
  • quaternized and/or protonated nitrogen-containing catalysts especially quaternized and/or protonated tertiary amines, are used.
  • quaternizing reagents for possible quaternization of nitrogen-containing catalysts, it is possible to use any reagents known as quaternizing reagents. Preference is given to using alkylating agents such as dimethyl sulfate, methyl chloride or benzyl chloride, preferably methylating agents such as, in particular, dimethyl sulfate, as quaternizing agents. Quaternization can likewise be carried out using alkylene oxides, such as ethylene oxide, propylene oxide or butylene oxide, preferably with subsequent neutralization using inorganic or organic acids.
  • alkylating agents such as dimethyl sulfate, methyl chloride or benzyl chloride
  • methylating agents such as, in particular, dimethyl sulfate
  • Quaternization can likewise be carried out using alkylene oxides, such as ethylene oxide, propylene oxide or butylene oxide, preferably with subsequent neutralization using inorganic or organic acids.
  • Nitrogen-containing catalysts may be singly or multiply quaternized. Preferably, the nitrogen-containing catalysts are only singly quaternized. In the case of single quaternization, the nitrogen-containing catalysts are preferably quaternized on a tertiary nitrogen atom.
  • Nitrogen-containing catalysts can be converted to the corresponding protonated compounds by reaction with organic or inorganic acids. These protonated compounds may be preferable, for example, when a slowed polyurethane reaction is to be achieved or when the reaction mixture is to have enhanced flow behaviour in use.
  • Organic acids used may, for example, be any organic acids mentioned below, for example carboxylic acids having from 1 to 36 carbon atoms (aromatic or aliphatic, linear or branched), such as formic acid, lactic acid, 2-ethylhexanoic acid, salicylic acid and neodecanoic acid, or else polymeric acids such as polyacrylic or polymethacrylic acids.
  • Inorganic acids used may, for example, be phosphorus- based acids, sulfur-based acids or boron-based acids.
  • Suitable metal compounds as catalysts are all metal compounds according to the prior art which catalyze one of the abovementioned isocyanate reactions and/or can be used for production of polyurethanes, especially of polyurethane foams. They may be selected, for example, from the group of metal- organic or organometallic compounds, metal-organic or organometallic salts, organic metal salts, inorganic metal salts, and from the group of charged or uncharged metallic coordination compounds, especially metal chelate complexes.
  • metal-organic or organometallic compounds in the context of this invention especially encompasses the use of metal compounds having a direct carbon-metal bond, also referred to here as metal organyls (e.g. tin organyls) or organometallic compounds (e.g. organotin compounds).
  • organometallic or metal-organic salts in the context of this invention especially encompasses the use of metal-organic or organometallic compounds having salt character, i.e. ionic compounds in which either the anion or cation is organometallic in nature (e.g. organotin oxides, organotin chlorides or organotin carboxylates).
  • organic metal salts in the context of this invention especially encompasses the use of metal compounds which do not have any direct carbon-metal bond and are simultaneously metal salts, in which either the anion or the cation is an organic compound (e.g. tin(ll) carboxylates).
  • organic metal salts in the context of this invention especially encompasses the use of metal compounds or of metal salts in which neither the anion nor the cation is an organic compound, e.g. metal chlorides (e.g. tin(ll) chloride), pure metal oxides (e.g. tin oxides) or mixed metal oxides, i.e.
  • coordination compound in the context of this invention especially encompasses the use of metal compounds formed from one or more central particles and one or more ligands, the central particles being charged or uncharged metals (e.g. metal- or tin-amine complexes).
  • metal-chelate complexes encompasses especially the use of metal-containing coordination compounds which have ligands having at least two coordination or bonding positions to the metal centre (e.g. metal- or tin-polyamine or metal- or tin-polyether complexes).
  • Suitable metal compounds may be selected, for example, from all metal compounds containing lithium, sodium, potassium, magnesium, calcium, scandium, yttrium, titanium, zirconium, vanadium, niobium, chromium, molybdenum, tungsten, manganese, cobalt, nickel, copper, zinc, mercury, aluminium, gallium, indium, germanium, tin, lead, and/or bismuth, especially sodium, potassium, magnesium, calcium, titanium, zirconium, molybdenum, tungsten, zinc, aluminium, tin and/or bismuth, more preferably tin, bismuth, zinc and/or potassium.
  • Suitable organometallic salts and organic metal salts, especially as defined above, as catalysts in the context of the present invention are, for example, organotin, tin, zinc, bismuth and potassium salts, in particular corresponding metal carboxylates, alkoxides, thiolates and mercaptoacetates, for example dibutyltin diacetate, dimethyltin dilaurate, dibutyltin dilaurate (DBTDL), dioctyltin dilaurate (DOTDL), dimethyltin dineodecanoate, dibutyltin dineodecanoate, dioctyltin dineodecanoate, dibutyltin dioleate, dibutyltin bis(n-lauryl mercaptide), dimethyltin bis(n-lauryl mercaptide), monomethyltin tris(2-ethylhexyl mercaptoacetate), dimethyltin bis
  • organometallic salts for example of dibutyltin dilaurate.
  • Suitable possible metallic catalysts are preferably selected such that they do not have any troublesome intrinsic odour and are essentially toxicologically safe, and such that the resulting polyurethane systems, especially polyurethane foams, preferably have a minimum level of catalyst- related emissions.
  • Preferred catalysts of this kind may be selected, for example, from the group of the metal compounds, preferably from the group of the tin, zinc, bismuth and/or potassium compounds, especially from the group of the metal carboxylates of the aforementioned metals, for example the tin, zinc, bismuth and/or potassium salts of isononanoic acid, neodecanoic acid, ricinoleic acid and/or oleic acid, and/or from the group of the nitrogen compounds, especially from the group of the low-emission amines and/or the low-emission compounds containing one or more tertiary amine groups, for example described by the amines dimethylaminoethanol, N,N-dimethyl-N',N'-di(2-hydroxypropyl)-1 ,3-diaminopropane
  • a preferred inventive process is characterized in that the one or more catalysts are selected from the group of nitrogen-containing compounds preferably amines, especially tertiary amines or compounds containing one or more tertiary amine groups, including triethylenediamine, 1 ,4- diazabicyclo[2.2.2]octane-2-yl-methanol, diethanolamine and compounds of the general formula (5)
  • X’ represents oxygen, nitrogen, hydroxyl, amines (NR 3’ or NR 3’ R 4’ ) or urea (N(R 5’ )C(0)N(R 6 ) or N (R 5 ) C (O) N R 6 R 7 )
  • Y’ represents amine NR 8’ R 9’ or ether OR 9’
  • R 1’ , R 2’ represent identical or different aliphatic or aromatic linear or cyclic hydrocarbon radicals having 1 - 8 carbon atoms optionally bearing an OH-group or representing hydrogen
  • R 3’ to R 9’ represent identical or different aliphatic or aromatic linear or cyclic hydrocarbon radicals having 1 - 8 carbon atoms optionally bearing an OH or a NH or NH2 group or representing hydrogen.
  • one or more catalysts are selected from the group of the low-emission amines and/or the low- emission compounds containing one or more tertiary amine groups preferably having a molar mass in the range between 160 and 500 g/mol and/or bearing a functionality reactive with the polyurethane matrix, preferably an isocyanate-reactive functionality, especially preferably NH or Nhh or OH, then that corresponds to a preferred embodiment of the invention.
  • one or more catalysts are selected from the group of the metal-organic or organometallic compounds, metal-organic or organometallic salts, organic metal salts, inorganic metal salts, and from the group of the charged or uncharged metallic coordination compounds, especially the metal chelate complexes, more preferably selected from the group of incorporable/reactive or high molecular weight metal catalysts, further preferred selected from the group tin, zinc, bismuth and/or potassium compounds, especially from the group of the metal carboxylates of the aforementioned metals, for example the tin, zinc, bismuth and/or potassium salts of isononanoic acid, neodecanoic acid, ricinoleic acid and/or oleic acid, then that corresponds to a preferred embodiment of the invention.
  • Such catalysts and/or mixtures are supplied commercially, for example, under the following names: Jeffcat ® ZF-10, Lupragen ® DMEA, Lupragen ® API, Toyocat ® RX 20 and Toyocat ® RX 21 , DABCO ® RP 202, DABCO ® RP 204, DABCO ® NE 300, DABCO ® NE 310, DABCO ® NE 400, DABCO ® NE 500, DABCO ® NE 600, DABCO ® NE 650, DABCO ® NE 660, DABCO ® NE 740, DABCO ® NE 750, DABCO ® NE 1060, DABCO ® NE 1080, DABCO ® NE 1082 and DABCO ® NE 2039, DABCO ® NE 1050, DABCO ® NE 1070, DABCO ® NE 1065; DABCO ® T, POLYCAT ®
  • one or more nitrogen-containing and/or metallic catalysts are used.
  • the catalysts may be used in any desired mixtures with one another. It is possible here to use the catalysts individually during the foaming operation, for example in the manner of a preliminary dosage in the mixing head, and/or in the form of a premixed catalyst combination.
  • catalyst combination for the purposes of this invention especially encompasses ready-made mixtures of metallic catalysts and/or nitrogenous catalysts and/or corresponding protonated and/or quaternized nitrogenous catalysts, and optionally also further ingredients or additives, for example water, organic solvents, acids for blocking the amines, emulsifiers, surfactants, blowing agents, antioxidants, flame retardants, stabilizers and/or siloxanes, preferably polyether siloxanes, which are already present as such prior to the foaming and therefor are not added as individual components during the foaming operation.
  • ingredients or additives for example water, organic solvents, acids for blocking the amines, emulsifiers, surfactants, blowing agents, antioxidants, flame retardants, stabilizers and/or siloxanes, preferably polyether siloxanes, which are already present as such prior to the foaming and therefor are not added as individual components during the foaming operation.
  • the sum total of all the nitrogen-containing catalysts used relative to the sum total of the metallic catalysts, especially potassium, zinc and/or tin catalysts results in a molar ratio of 1 :0.05 to 0.05:1 , preferably 1 :0.07 to 0.07:1 and more preferably 1 :0.1 to 0.1 :1.
  • Optional additives used may be all substances which are known according to the prior art and find use in the production of polyurethanes, especially of hot-cure flexible PU foams, for example blowing agents, preferably water for formation of CO2, and, if necessary, further physical blowing agents, crosslinkers and chain extenders, stabilizers against oxidative degradation (called antioxidants), flame retardants, surfactants, biocides, cell-refining or coarsening additives, cell openers, solid fillers, antistatic additives, nucleating agents, thickeners, dyes, pigments, colour pastes, fragrances, emulsifiers, buffer substances and/or catalytically active substances, especially as defined above.
  • blowing agents preferably water for formation of CO2
  • further physical blowing agents preferably water for formation of CO2
  • further physical blowing agents preferably water for formation of CO2
  • antioxidants stabilizers against oxidative degradation
  • flame retardants flame retardants
  • surfactants biocides
  • suitable physical blowing agents are, for example, liquefied CO2 and volatile liquids, for example hydrocarbons having 3, 4 or 5 carbon atoms, preferably cyclopentane, isopentane and n-pentane, oxygen-containing compounds such as methyl formate, acetone and dimethoxymethane, or chlorinated hydrocarbons, preferably dichloromethane and 1 ,2- dichloroethane.
  • organomodified siloxanes are preferably used in the production of the different types of PU foams.
  • (Organomodified) siloxanes suitable for this purpose are described for example in the following documents: EP 0839852, EP 0780414, EP 0867465, EP 1544235, EP 1553127, EP 0533202, US 3933695, EP 1753799, US 20070072951 , DE 2533074. These compounds may be prepared as described in the prior art. Suitable examples are described, for instance, in US 4147847, EP 0493836, EP 1520870, EP 0600261 , EP 0585771 , EP 0415208 and US 3532732.
  • Foam stabilizers for the production of hot-cure flexible PU foams are preferably characterized by large siloxane structures preferably having more than 50 Si units and pendant polyethers. These foam stabilizers are also referred to as polydialkylsiloxane-polyoxyalkylene copolymers. The structure of these compounds is preferably such that, for example, a long-chain copolymer of ethylene oxide and propylene oxide is bonded to a polydimethylsiloxane radical. The linkage between the polydialkylsiloxane and the polyether moiety may be via SiC or Si-O-C linkage.
  • the polyether moieties are built up from the monomers propylene oxide, ethylene oxide, butylene oxide and/or styrene oxide in blocks or in random distribution, and may either be hydroxy- functional or end-capped by a methyl ether function or an acetoxy function.
  • the molecular masses of the polyether moieties are preferably in a range of 150 to 8000 g/mol.
  • the polyether or the different polyethers may be bonded to the polydialkylsiloxane in terminal or lateral positions.
  • the alkyl radical of the siloxane may be aliphatic, cycloaliphatic or aromatic. Methyl groups are very particularly advantageous.
  • the organomodified polydialkylsiloxane may be linear or else contain branches.
  • Suitable stabilizers, especially foam stabilizers, are described inter alia in US 2834748, US2917480 and in US3629308.
  • the function of the foam stabilizer is to assure the stability of the foaming reaction mixture.
  • the contribution to foam stabilization correlates here with siloxane chain length. Without foam stabilizer, a collapse is observed, and hence no homogeneous foam is obtained.
  • some flexible PU foam types not according to the invention that have higher stability and hence a lower tendency to collapse, it is also possible to use low molecular weight polyethersiloxanes. These then have siloxane chain lengths much shorter than 50.
  • the inventive compound of formula (1) which was described above, is a foam stabilizer.
  • further foam stabilizers according to formula (6) which are different from the compound of formula (1), may be used additionally.
  • no further foam stabilizers which are different from the compound of formula (1), are used.
  • Optional foam stabilizers according to formula (6) are in accordance with the following structure:
  • R 1 same or different radicals, selected from the group of alkyl radicals having 1 - 16 carbon atoms or aryl radicals having 6 - 16 carbon atoms or hydrogen or -OR 5 ” , saturated or unsaturated, preferably methyl, ethyl, octyl, dodecyl, phenyl or hydrogen, more preferably methyl or phenyl
  • R 2 independently identical or different polyethers obtainable from the polymerization of ethylene oxide, propylene oxide and/or other alkylene oxides such as butylene oxide or styrene oxide of the general formula (7) or an organic radical according to formula (8)
  • R 4 divalent organic radical, preferably a divalent organic alkyl or
  • R 5 same or different radicals, selected from the group of alkyl radicals having 1 - 16 carbon atoms or aryl radicals having 6 - 16 carbon atoms, saturated or unsaturated, or hydrogen, preferably alkyl radicals having 1 - 8 carbon atoms, saturated or unsaturated, or hydrogen, more preferably methyl, ethyl, isopropyl or hydrogen
  • R 6 same or different radicals, selected from the group of alkyl radicals having 1 - 18 carbon atoms, and optionally bearing ether functions or substitution with halogen atoms, or aryl radicals having 6 - 18 carbon atoms and optionally bearing ether functions, or hydrogen, preferably alkyl radicals having 1 - 12 carbon atoms, and optionally bearing ether functions or substitution with halogen atoms, or aryl radicals having 6 - 12 carbon atoms and optionally bearing ether functions, or hydrogen, more preferably hydrogen, methyl, ethyl or benzyl
  • R 7 same or
  • R 8 same or different radicals, selected from the group or alkyl radicals or aryl radicals, saturated or unsaturated, and optionally bearing one or more OH, ether, epoxide, ester, amine or/and halogen substituents, preferably alkyl radicals having 1 - 18 carbon atoms or aryl radicals having 6 - 18 carbon atoms, saturated or unsaturated, and optionally bearing one or more OH, ether, epoxide, ester, amine or/and halogen substituents, more preferably alkyl radicals having 1 - 18 carbon atoms or aryl radicals having 6 - 18 carbon atoms, or aryl radicals having 6 - 12 carbon atoms, saturated or unsaturated, bearing at least one substituent selected of the group of OH, ether, epoxide, ester, amine or/and halogen substituents
  • R 9 same or different radicals, selected from the group of alkyl radicals having 1 -
  • siloxanes of formula (1) and further foam stabilizers according to formula (6) can contain a low amount of cyclic siloxanes, which means that the total content of the sum of cyclotetrasiloxane (D4), cyclopentasiloxane (D5) and cyclohexasiloxane (D6) is not higher than 0,1% by weight. In a particularly preferred embodiment of the invention, the total content of D4, D5 and D6 is not higher than 0,07% by weight. It is also possible to use the siloxanes of formula (1) and formula (6) as blends with e.g. suitable solvents and/or further additives. As optional solvents, it is possible to employ all suitable substances known from the prior art.
  • aprotic nonpolar, aprotic polar and protic solvents can, for example, be selected from the following classes of substances, or classes of substances containing the following functional groups: aromatic hydrocarbons, aliphatic hydrocarbons (alkanes (paraffins) and olefins), carboxylic esters (e.g. isopropyl myristate, propylene glycol dioleate, decyl cocoate or other esters of fatty acids) and polyesters, (poly)ethers and/or halogenated hydrocarbons having a low polarity.
  • aromatic hydrocarbons aliphatic hydrocarbons (alkanes (paraffins) and olefins)
  • carboxylic esters e.g. isopropyl myristate, propylene glycol dioleate, decyl cocoate or other esters of fatty acids
  • polyesters e.g. isopropyl myristate, propylene glycol dioleate, dec
  • Suitable aprotic polar solvents can, for example, be selected from the following classes of substances, or classes of substances containing the following functional groups: ketones, lactones, lactams, nitriles, carboxamides, sulfoxides and/or sulfones.
  • Suitable protic solvents can, for example, be selected from the following classes of substances, or classes of substances containing the following functional groups: alcohols, polyols, (poly)alkylene glycols, amines, carboxylic acids, in particular fatty acids and/or primary and secondary amides. Particular preference is given to solvents which are readily employable in the foaming operation and do not adversely affect the properties of the foam.
  • isocyanate-reactive compounds are suitable, since they are incorporated into the polymer matrix by reaction and do not generate any emissions in the foam.
  • examples are OH-functional compounds such as (poly)alkylene glycols, preferably monoethylene glycol (MEG or EG), diethylene glycol (DEG), triethylene glycol (TEG), 1 ,2-propylene glycol (PG), dipropylene glycol (DPG), trimethylene glycol (propane-1 ,3-diol, PDO), tetramethylene glycol (butanediol, BDO), butyl diglycol (BDG), neopentyl glycol, 2-methylpropane-1 ,3-diol (ORTEGOL ® CXT) and higher homologues thereof, for example polyethylene glycol (PEG) having average molecular masses between 200 g/mol and 3000 g/mol.
  • PEG polyethylene glycol
  • Particularly preferred OH-functional compounds further include polyethers having average molecular masses of 200 g/mol to 4500 g/mol, especially 400 g/mol to 2000 g/mol, among these preferably water-, allyl-, butyl- or nonyl-initiated polyethers, in particular those which are based on propylene oxide (PO) and/or ethylene oxide (EO).
  • polyethers having average molecular masses of 200 g/mol to 4500 g/mol, especially 400 g/mol to 2000 g/mol among these preferably water-, allyl-, butyl- or nonyl-initiated polyethers, in particular those which are based on propylene oxide (PO) and/or ethylene oxide (EO).
  • PO propylene oxide
  • EO ethylene oxide
  • Optional crosslinkers and optional chain extenders are low molecular weight, polyfunctional compounds which are reactive toward isocyanates.
  • Suitable compounds are, for example, hydroxyl- or amine-terminated substances such as glycerol, neopentyl glycol, 2-methyl-1 ,3-propanediol, triethanolamine (TEOA), diethanolamine (DEOA) and trimethylolpropane.
  • TEOA triethanolamine
  • DEOA diethanolamine
  • trimethylolpropane trimethylolpropane.
  • the use concentration can preferably be in the range from 0.1 to 5 parts, based on 100 parts of polyol, but can also deviate therefrom depending on the formulation.
  • Suitable optional stabilizers against oxidative degradation preferably include all common free-radical scavengers, peroxide scavengers, UV absorbers, light stabilizers, complexing agents for metal ion impurities (metal deactivators).
  • substituents on the respective parent molecules preferably being, in particular, substituents which have groups which are reactive toward isocyanate: 2-(2'- hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, benzoic acids and benzoates, phenols, in particular comprising tert-butyl and/or methyl substituents on the aromatic entity, benzofuranones, diarylamines, triazines, 2,2,6,6-tetramethylpiperidines, hydroxylamines, alkyl and aryl phosphites, sulfides, zinc carboxylates, diketones.
  • Phenols may, for example, be esters based on 3-(4- hydroxyphenyl)propionic acid such as triethylene glycol bis(3-tert-butyl-4-hydroxy-5- methylphenyl)propionate, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, or methylenediphenols such as 4,4‘-butylidenebis(6-tert-butyl-3-methylphenol).
  • 3-(4- hydroxyphenyl)propionic acid such as triethylene glycol bis(3-tert-butyl-4-hydroxy-5- methylphenyl)propionate, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, or methylenediphenols such as 4,4‘-butylidenebis(6-tert-butyl-3-methylphenol).
  • Preferred 2-(2’- hydroxyphenyl)benzotriazoles are, for example, 2-(2’-hydroxy-5’-methylphenyl)benzotriazole or 2- (2’-hydroxy-3‘,5‘-di-tert-butylphenyl)benzotriazole.
  • Preferred 2-hydroxybenzophenones are, for example, 2-hydroxy-4-n-octoxybenzophenone, 2,2‘,4,4‘-tetrahydroxybenzophenone or 2,4- dihydroxybenzophenone.
  • Preferred benzoates are, for example, hexadecyl 3,5-di-tert-butyl-4- hydroxybenzoate or tannins.
  • Suitable optional flame retardants in the context of this invention are all substances which are regarded as suitable for this purpose according to the prior art.
  • Preferred flame retardants are, for example, liquid organophosphorus compounds such as halogen-free organophosphates, e.g. triethyl phosphate (TEP), halogenated phosphates, for example tris(1-chloro-2-propyl) phosphate (TCPP) and tris(2-chloroethyl) phosphate (TCEP), and organic phosphonates, for example dimethyl methanephosphonate (DMMP), dimethyl propanephosphonate (DMPP), or solids such as ammonium polyphosphate (APP) and red phosphorus.
  • Suitable flame retardants further include halogenated compounds, for example halogenated polyols, and also solids such as expandable graphite and melamine.
  • Optional Biocides used may, for example, be commercial products such as chlorophene, benzisothiazolinone, hexahydro-1 ,3,5-tris(hydroxyethyl-s-triazine), chloromethylisothiazolinone, methylisothiazolinone or 1 ,6-dihydroxy-2,5-dioxohexane, which are known under the trade names BIT 10, Nipacide BCP, Acticide MBS, Nipacide BK, Nipacide Cl, Nipacide FC.
  • the hot-cure flexible PU foams according to the invention can be produced by any methods familiar to the person skilled in the art, for example by manual mixing or preferably with the aid of foaming machines, especially low-pressure or high-pressure foaming machines. Batch processes or continuous processes may be used here.
  • hot-cure flexible PU foams it is possible to use any methods known to the person skilled in the art for production of hot-cure flexible PU foams.
  • the foaming operation can be affected either in the horizontal or in the vertical direction, in batchwise plants or continuous plants.
  • the compositions used in accordance with the invention may similarly be used for CO2 technology.
  • Use in low-pressure and high-pressure machines is possible, with the compositions to be processed being able to be metered directly into the mixing chamber or be admixed even before the mixing chamber with one of the components which then go into the mixing chamber. Admixture in the raw material tank is also possible.
  • a particularly preferred hot-cure flexible PU foam for the purpose of the present invention especially has the following composition:
  • (Amine) catalyst 0.05 to 5 Tin catalyst 0 to 5, preferably from 0.01 to 2 at least one compound of formula (1) 0.07 to 6.0, preferably 0.10 to 5.0 Physical blowing agent 0 to 130 Flame retardant O to 70 Fillers 0 to 150
  • foam stabilizer * 0 to 6.0, preferably 0 to 5.0
  • Another subject of the invention is a process for storing and/or for transporting shaped hot-cure flexible PU foam articles, preferably mattresses and/or cushions, where
  • a shaped hot-cure flexible PU foam article is provided by reaction of at least one polyol component and at least one isocyanate component in the presence of at least one blowing agent and of at least one catalyst and further additives, wherein the additives comprise at least one foam stabilizer, which is a compound of formula (1), as defined in claim 1 ,
  • the shaped hot-cure flexible PU foam article obtained may optionally be subjected to further processing to prepare it for the application,
  • the shaped hot-cure flexible PU foam article (optionally prepared for the application) is compressed by at least 20%, preferably 30%, especially 40%, based on its starting volume, and optionally vacuum-packed and kept in compressed form by auxiliary means, in particular packaging means, and sent for storage and/or transport.
  • this process is characterized in that a sufficient amount of the inventive compound of formula (1), as defined in claim 1 , is added in step (a) so that the proportion by mass thereof in the finished polyurethane foam is from 0.05 % to 3.0 % by weight, preferably from 0.07 % to 2.5 % by weight, more preferably 0.10 % to 2.0 % by weight.
  • Another subject of the invention is a process for producing flexible hot-cure polyurethane foam by reaction of at least one polyol component and at least one isocyanate component in the presence of at least one blowing agent and of at least one catalyst and further additives, wherein the additives comprise at least one foam stabilizer, which is a compound of formula (1), as defined in claim 1 , preferably with additional use of recycled polyols.
  • the flexible hot-cure PU foam is a standard flexible PU foam, viscoelastic PU foam or a hypersoft PU foam.
  • reaction to produce the inventive flexible hot-cure PU foams is effected using
  • one or more foam stabilizers based on polydialkylsiloxane-polyoxyalkylene copolymers, and/or • one or more further auxiliaries, preferably selected from the group of the surfactants, biocides, dyes, pigments, fillers, antistatic additives, crosslinkers, chain extenders, cell openers and/or fragrances.
  • the invention further provides a flexible hot-cure polyurethane foam, preferably a standard flexible PU foam, viscoelastic PU foam or hypersoft PU foam, which is obtainable by a process as described above.
  • An inventive flexible hot-cure PU foam wherein the foam has a rebound resilience of 1-50%, measured in accordance with DIN EN ISO 8307:2008-03, and/or a foam density of 5 to 150 kg/m3 and/or a porosity, optionally after crushing the foams, of 0.5 to 6 scfm, preferably 1.0 to 6.0 scfm, corresponds to a preferred embodiment of the invention.
  • the invention further provides the use of the inventive hot-cure flexible PU foams as packaging foam, mattress, furniture cushion, automobile seat cushion, headrest, dashboard, automobile interior trim, automobile roof liner, sound absorption material, or for production of corresponding products.
  • the invention further provides the use of at least one compound of formula (1), as defined in claim 1 , for improving the dimensional recovery of shaped hot-cure flexible PU foam articles after compression thereof over a period of at least 20 hours, wherein the shaped hot-cure flexible PU foam article is obtainable by reaction of at least one polyol component and at least one isocyanate component in the presence of at least one blowing agent and of at least one catalyst and further additives.
  • the invention further provides the use of flexible polyurethane foam in mattresses and/or cushions, especially mattresses, wherein the flexible hot-cure PU foam has been obtained by reaction of at least one polyol component and at least one isocyanate component in the presence of one or more catalysts that catalyze the isocyanate-polyol and/or isocyanate-water reactions and/or isocyanate trimerization and further additives, characterized in that the additives comprise at least one foam stabilizer, which is a compound of formula (1), as defined in claim 1 , preferably with additional use of recycled polyols.
  • GPC measurements of foam stabilizers The polydispersity and the molar mass averages M n and M of the non-inventive and inventive foam stabilizers were determined by gel permeation chromatography (GPC) based on ISO 13885-1 :2020 under the following conditions: separation column combination SDV 1000/10000 A with precolumn (length: 65 cm, column temperature: 30 °C), THF as mobile phase, flow rate: 1 ml/min, sample concentration: 10 g/L, injection volume 20 pi, refractive index (Rl) detector (30 °C), calibration with polystyrene (162 - 2520000 g/mol). The obtained values are polystyrene molar mass equivalents.
  • the flexible PU foams produced were assessed according to the following physical properties a) to 9): a) Rise time: The period of time between the end of mixing of the reaction components and the blow-off of the polyurethane foam. b) Rise height or foam height: the height of the free-risen foam formed after 3 minutes. Foam height is reported in centimetres (cm). c) Settling of the foam at the end of the rise phase: The settling is calculated from the difference of the foam height after direct blow-off and 3 minutes after foam blow-off. The foam height is measured at the maximum in the middle of the foam crest by means of a needle secured to a centimetre scale.
  • a negative value here describes settling of the foam after blow-off; a positive value correspondingly describes further rise of the foam.
  • test specimens having dimensions of 5 cm c 5 cm c 2.5 cm were cut out of each of the finished foams transverse to the direction of rise of the foam, and successively inserted into an analytical instrument constructed for this method.
  • the construction of this instrument is described in ASTM D 3574 (2011-00).
  • the analytical instrument generates an air pressure differential of 125 Pa between the inside of the instrument and the surrounding atmosphere by sucking just enough air in through the test specimen for the differential to be kept constant.
  • the air flow through the test specimen is thus a measure of the porosity of the foam. Values in the range from 0-6.5 scfm (standard cubic feet per min) were measured, with lower values within the interval characterizing a more tight foam and higher values a more open foam.
  • Result of the rolling test This specific test is described in detail below.
  • the materials are characterized here regarding the type and the amount of the organic substances outgassable therefrom.
  • the analysis method serves to ascertain emissions from materials that are used in furniture and mattresses. This is done by using test chambers to measure the emissions.
  • Test specimen sample preparation, sampling and specimen dimensions
  • the reaction mixture is introduced into a PE plastic bag which is open at the top. After the foam has risen and blown off, the PE bag is closed 3 min after the blow-off. The foam is stored in this way at room temperature for 12 hours in order to enable complete reaction, but simultaneously in order to prevent premature escape of VOCs. Subsequently, the PE bag is opened and a 7 cm x 7 cm x 7 cm cube is taken from the centre of the foam block and immediately wrapped in aluminium foil and sealed airtight in a PE bag. It was then transported to the analytical laboratory, and the foam cube was introduced into a cleaned 30 I glass test chamber. The conditions in the test chamber were controlled climatic conditions (temperature 21 °C, air humidity 50%). Half the volume of the test chamber is exchanged per hour.
  • VOC adsorption tubes serve to absorb the VOCs.
  • the Tenax tube is then heated, and the volatile substances released are cryofocused in a cold trap of a temperature-programmable evaporator with the aid of an inert gas stream. After the heating phase has ended, the cold trap is rapidly heated to 280°C.
  • the focused substances vaporize in the process. They are subsequently separated in the gas chromatography separation column and detected by mass spectrometry. Calibration with reference substances permits a semi-quantitative estimate of the emission, expressed in “pg/m 3 ”.
  • the quantitative reference substance used for the VOC analysis (VOC value) is toluene.
  • Signal peaks can be assigned to substances using their mass spectra and retention indices.
  • the following equipment is used for the analysis: Gerstel, D-45473 Miihlheim an der Ruhr, Eberhard-Gerstel-Platz 1 , Germany, TDS-3 / KAS-4, Tenax® desorption tubes, Agilent Technologies 7890A (GC) / 5975C (MS), column: HP Ultra2 (50 m, 0.32 mm, 0.52 pm), carrier gas: helium. More specific procedural instructions can be taken from DIN EN ISO 16000-9:2008-04.
  • VDA 278 analytical principles
  • the materials are characterized regarding the type and the amount of the organic substances outgassable therefrom.
  • two semi-quantitative empirical values are determined to estimate the emission of volatile organic compounds (VOC value) and also the proportion of condensable substances (fogging value). Individual substances ofthe emission are also determined.
  • the samples are thermally extracted and the emissions are separated by gas chromatography and detected by mass spectrometry.
  • the overall concentrations thus obtained for the VOC fraction are arithmetically converted into toluene equivalents and provide the VOC value as a result; the FOG fraction is represented in hexadecane equivalents and provides the FOG value.
  • the analytical method serves to determine emissions from non-metallic materials used for moulded parts in motor vehicles; they also include foams.
  • TDS thermal desorption analysis
  • small amounts of material are heated up in a desorption tube in a defined manner and the volatile substances which are emitted in the course of heating are cryofocused by means of an inert gas stream in a cold trap of a temperature-programmable vaporizer. After the heating phase has ended, the cold trap is rapidly heated to 280°C.
  • the focused substances vaporize in the process. They are subsequently separated in the gas-chromatographic separation column and detected by mass spectrometry. Calibration with reference substances permits a semi-quantitative estimate of the emission, expressed in “pg/g”.
  • the quantitative reference substances used are toluene for the VOC analysis (VOC value) and n-hexadecane for the fogging value. Signal peaks can be assigned to substances using their mass spectra and retention indices.
  • the test has for its object to simulate the conditions of rolled mattresses in the laboratory. Since there is no meaningful industry standard for this a novel test was developed which simulates the rolling-up of mattress foams on a small scale.
  • Test specimens having dimensions of 12 cm (width), 16 cm (length) and 2.5 cm (thickness) are cut out of the flexible PU foam blocks as obtained from manual foaming for example, using a band saw. A central position in the foam blocks from manual foaming is selected. The test specimen is cut out such that the rise direction of the foam during production is at right angles to the length and width of the test specimen. Test specimens are marked with a felt pen. Test procedure:
  • the test specimen is compressed with a thin metal rod of diameter 5-8 mm (e.g. metal ballpoint pen) at a 12 cm edge.
  • the foam test specimen is then rolled up around this metal rod by hand. This significantly compresses the foam, forming a roll having a diameter of about 3-4 cm. This roll is held manually in this compressed state and pushed completely into a cardboard tube.
  • the cardboard tube has an internal diameter of 4 cm and a length of at least 13 cm.
  • the metal rod may be lightly greased before the rolling of the foam.
  • the foam then fills the volume of the tube. The compression of the foam in the centre is much more severe than at the edge of the tube.
  • the roll is then stored under controlled, constant conditions (temperature: 21 °C, atmospheric humidity: 60%) for 7 days. After 168 hours the foam is manually removed from the tube and placed on an even surface, and the unrolling of the foam is observed. The expansion of the foam must not be disturbed or influenced.
  • the shaped flexible PU foam article is left to expand for 10 minutes.
  • the test specimens are then evaluated. The most important criterion is whether the foam has completely recovered its original thickness or - especially at the more severely compressed edge - still has compression zones. In some cases, a groove from the compression is also apparent on the surface of the test specimen. Very poor test specimens remain rolled up at one end. A slight bend in the test specimen after expansion is normal and is not considered in the assessment. The following grades were used for the evaluation:
  • test specimen has regained a thickness of 2.5 cm at all sites. No indentations and grooves remain visible at the surface after 10 minutes (particularly at the more severely compressed end).
  • test specimen has regained a thickness of 2.5 cm at all sites. However, slight indentations and grooves remain visible at the surface (particularly at the more severely compressed end).
  • test specimen exhibits a slight compression at the more severely compressed end. The thickness there is more than 2.0 cm but less than 2.5 cm. An indentation is clearly visible at this end.
  • Test specimen exhibits a slight compression at the more severely compressed end. The thickness of the sample there is more than 1 cm but still considerably less than 2.0 cm.
  • Test specimen exhibits a severe compression at the more severely compressed end.
  • the thickness of the sample there is less than 1 cm.
  • the sample is still partly rolled up at this end.
  • Test specimen remains rolled up and compressed at the more severely compressed end.
  • the evaluation is preferably performed by at least two people.
  • the results are documented. In the context of the present invention the evaluation was carried out by four people who arrived at consistent results.
  • the foam test specimen must have constant cell structure parameters, i.e. in particular a constant cell size and a constant air permeability.
  • the metal rod must not be excessively greased so that no grease penetrates into the sample. Constant storage conditions must be maintained. Test specimens given the various evaluation grades must be kept available for comparison.
  • Hot-cure flexible PU foam - foaming examples are:
  • Example 1 Production of hot-cure flexible PU foams (flexible slabstock foam)
  • Table 1 Formulation 1 for hot-cure flexible PU foam production.
  • Tin catalyst 2 0.20-0.28 TEGOAMIN ® DMEA 3) 0.15 FOAM STABILIZER 4 » 0.45 Desmodur ® T 80 5) 50.0
  • KOSMOS ® T9 available from Evonik Industries: tin(ll) salt of 2-ethylhexanoic acid.
  • Foam stabilizer non-inventive polyether-modified polysiloxane or inventive polyether-modified polysiloxanes, according to formula (1).
  • the polyether-modified polysiloxanes were obtained by the following synthesis procedures: Foam stabilizer 1 (non-inventive):
  • Foam stabilizer 2 (inventive ' ):
  • Foam stabilizer 4 (inventive ' ):
  • tolylene diisocyanate T 80 (80% 2,4 isomer, 20% 2,6 isomer) from Covestro, 3 mPa-s, 48% NCO, functionality 2. 400 g of polyol was used in each foaming operation; the other formulation constituents were recalculated accordingly. 1.00 part of a component denoted 1.00 g of this substance per 100 g of polyol for example.
  • the foaming was carried out by what is called manual mixing.
  • Formulation 1 as specified in table 1 was used.
  • a paper cup was charged with polyol, the respective amine catalyst mixture, the tin catalyst tin(ll) 2-ethylhexanoate, water and a foam stabilizer, and the contents were mixed at 1000 rpm for 60 seconds with a disc stirrer.
  • the isocyanate (TDI) was added to the reaction mixture and stirred at 2500 rpm for 7 s and then immediately transferred into a paper- lined box (30 cm x 30 cm base area and 30 cm height). After being poured in, the foam rose in the foaming box. In the ideal case, the foam blew off on attainment of the maximum rise height and then fell back slightly.
  • Hot-cure flexible PU foams were produced with a standard flexible foam stabilizer (foam stabilizer 1) and with the inventive flexible foam stabilizers 2, 3 and 4.
  • Table 2 Reference foams (obtained using foam stabilizer 1) and foams with foam stabilizer 2.
  • the result of the rolling test depends significantly on the porosity of the foam. For foams having a more closed cell structure generally worse results are obtained than for those foams those having an open cell structure.
  • the screening was performed after adjustment of the foam porosity to different levels. This was achieved by variation of the use level of tin catalyst (KOSMOS ® T9) between 0.20 and 0.28 pphp. Foams obtained using the same use level of tin catalyst were compared with each other.
  • inventive foam stabilizers 2, 3 and 4 does not show any significant impact on general foam properties like porosity, cell structure or hardness, compared to the non-inventive foam stabilizer 1 , it was surprisingly found that the foams obtained using the inventive foam stabilizers show significantly improved results in the recovery after compression over the whole investigated porosity range, as tested by the rolling test. The recovery of the original shape of the test specimens after rolling deformation was improved to a quite crucial degree when comparing foams with similar porosities: e.g.
  • foam #1 and foam #4 were both obtained using 0.20 pphp KOSMOS ® T9 and show comparable foam properties, but while foam #1 (using non-inventive foam stabilizer 1) was rated with + in the rolling test (recovery of original sample height, but remaining indentations and grooves after 10 minutes), foam #4 using the inventive foam stabilizer 2 was surprisingly rated significantly better as + + + (fully recovered after less than 5 minutes). This improvement stands for a significantly better recovery of the rolled and compressed foam samples. The same significant improvement is also found for the tighter foams obtained using a higher level of KOSMOS ® T9 and for the foams obtained using foams stabilizers 3 and 4.
  • the hot-cure flexible PU foams according to the invention are also found to have low emissions.
  • the foam stabilizers 2, 3 and 4 are thus also highly suitable for use in low-emissions formulations. The results are summarized in table 4.
  • Table 4 Results of chamber tests according to DIN EN ISO 16000-9:2008-04 and VDA 278 for a reference hot-cure flexible PU foam obtained using foam stabilizer 1 and a foam using the inventive foam stabilizer 2 based on a low emission formulation.
  • VDA 278 Foam stabilizer 1 (non-inventive) ⁇ 10 pg/g

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

Article façonné en mousse PU souple à durcissement à température élevée, préférentiellement un matelas et/ou un coussin, la mousse PU souple ayant été obtenue par réaction d'au moins un composant polyol et d'au moins un composant isocyanate en présence d'au moins un agent gonflant et d'un ou de plusieurs catalyseurs qui catalysent les réactions isocyanate-polyol et/ou isocyanate-eau et/ou la trimérisation d'isocyanate, et d'un stabilisateur de mousse et d'autres additifs, caractérisé en ce que le stabilisateur de mousse comprend au moins un composé de formule (1) [R1 2R2SiO1/2]a [R1 3SiO1/2]b [R1 2SiO2/2]c [R1R2SiO2/2]d [R3SiO3/2]e [SiO4/2]f Gg.
EP22734246.6A 2021-06-17 2022-06-09 Articles façonnés en mousse pu souple Pending EP4355804A1 (fr)

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